KR950000040B1 - Fiber reactive monoazo compound having 7-substituted amino-1-naphthal-sulfonic acid as coupling compound - Google Patents

Abstract

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Description

Process for preparing monoazo compound in free acid form

The present invention relates to a process for the preparation of the monoazo compound in free acid form of the general formula (I) containing 7-substituted amino-1-naphtholmono- or di-sulfonic acid as coupling component.

의 그룹이고, R₄는 수소 또는 비치환되거나 치환된 저급 알킬이고, R₅는 수소 또는 설포이고, B₄는 일반식

(여기서, R₆는 수소, 염소, 설포, 카복시, 메틸, 메톡시 또는 에톡시이다)의 그룹 또는 구조식

의 그룹이고, X는 염소, 불소, 저급 알콕시, 비치환되거나 치환된 펜옥시, 또는 일반식

(여기서, R₇및 R₈은 서로 독립적으로 수소 또는 비치환되거나 치환된 저급 알킬, 페닐, 나프틸 또는 벤질 그룹이다.) :이고, A는 비치환되거나 치환된 페닐렌 또는 나프틸렌 그룹이며, Z는 -SO₂CH=CH₂또는 -SO₂CH₂CH₂Y(여기서 Y는 알칼리의 작용에 의해 분리가능한 그룹이다)의 그룹이다.Wherein R ₁ and R ₂ are independently of each other hydrogen or unsubstituted or substituted lower alkyl, and R ₃ is unsubstituted or substituted lower alkyl, acyl or structural formula

R ₄ is hydrogen or unsubstituted or substituted lower alkyl, R ₅ is hydrogen or sulfo, and B ₄ is a general formula

Wherein R ₆ is hydrogen, chlorine, sulfo, carboxy, methyl, methoxy or ethoxy

X is chlorine, fluorine, lower alkoxy, unsubstituted or substituted phenoxy, or a general formula

(Wherein R ₇ and R ₈ are independently of each other hydrogen or an unsubstituted or substituted lower alkyl, phenyl, naphthyl or benzyl group): and A is an unsubstituted or substituted phenylene or naphthylene group, Z is a -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ Y (wherein Y is a group detachable by the action of an alkali) group.

Several types of fiber-reactive dyes have been used to dye or print textile materials. Of these, transportable dyes having both vinylhalone type groups such as monohalogenotriazinyl groups and sulfatoethylsulfonyl groups in one molecule are prominent due to their improved dye performance. As reactive dyes of this kind useful for dyeing or printing textile materials in red, the monoazo compounds of the following structural formulas are described in Japanese Patent Application No. 199877/1982.

However, known red dyes of this kind, including the compounds of the above structural formulas, have not only dyeing properties such as build-up properties, insensitivity to changes in dyeing temperature, but also formalin fastness, formalin-daylight fastness and the like. There is still room for further improvement in dye performance as it is not yet satisfactory to meet the high requirements for the same fastness.

The inventors have made considerable research in order to find monoazo compounds that meet the above requirements.

(여기서, R₇및 R₈은 상기 정의한 바와 같다)의 그룹인, 일반식(Ⅰ)의 모노아조 화합물에 상응하는 하기 일반식(Ⅰ")의 모노아조 화합물을 수득함을 특징으로 하여, 일반식(Ⅰ)의 모노아조 화합을 제조하는 방법 및 일반식(I)의 모노아조 화합물 또는 이의 염을 제공한다.The present invention relates to (a) reacting a diazonium salt of an amine compound of the following general formula (IV) with a naphthol compound of the following general formula (V), or an aromatic amine compound of the following general formula (III) or Any one of the monoazo naphthol compounds of iii) is reacted with cyanurate or cyanuric acid fluoride and then with the other of the general formulas (III) and (iii), wherein X is a chlorine or fluorine atom, Obtaining the monoazo compound of the following general formula (I ') corresponding to the monoazo compound of the general formula (I); (b) reacting a monoazo compound of the general formula (I ') with a compound of the following general formula (VIII), or any one of the monoazo naphthol compound of the general formula (VIII) Reacted with cyanuric acid chloride or cyanuric acid fluoride, followed by reacting with the other of the compounds of formulas (iii) and (iii), followed by reaction with the aromatic amine compound of formula (III), where X is lower alkoxy, Unsubstituted or substituted phenoxy or a general formula

Characterized by obtaining a monoazo compound of the general formula (I ") corresponding to the monoazo compound of the general formula (I), wherein R ₇ and R ₈ are as defined above Provided are a process for preparing a monoazo compound of formula (I) and a monoazo compound of formula (I) or a salt thereof.

(여기서 R₇및 R₈은 상기 정의한 바와 같다)의 그룹이다.Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ A, B and Z are as defined above, X ₁ is chlorine or fluorine, X ₂ is lower alkoxy, unsubstituted or substituted phenoxy or General formula

Wherein R ₇ and R ₈ are as defined above.

In addition, the present invention provides a method of dyeing or printing a fiber material, using the monoazo compound of formula (I) or a salt thereof.

Preferred among these monoazo compounds of the general formula (I) are compounds of the following general formula.

Wherein R ₅ is as defined above, R ₁₀ is hydrogen methyl or ethyl, R ₁₁ is hydrogen, chlorine or sulfo, R ₁₂ is methyl, ethyl, acetyl or propionyl, and R ₁₃ is hydrogen, methyl or is ethyl, R ₁₄ is hydrogen or sulfo, and Z ₁ is _{-SO 2 CH = CH 2 = CH} 2 or _{-SO 2 CH 2 CH 2 OSO 3} H.

In the present invention, the lower alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ preferably means an alkyl group having 1 to 4 carbon atoms, and preferred substituents of the alkyl group are hydroxyl, cyano, C ₁ − C ₄ alkoxy, halogeno, carboxy, carbamoyl, C ₁ -C ₄ alkoxy carbonyl, C ₁ -C ₄ alkylcarbonyloxy, sulfo, sulfamoyl and the like. Preferred examples of the unsubstituted or substituted alkyl group represented by R ₁ , R ₂ , R ₃ , and R ₄ include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, secondary-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyano Methyl, 2-cyanoethyl, 3-cyanopropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 2-hydroxy -3-methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl , Ethoxycarbonylmethyl, 2-meth Cycarbonylethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, Ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, 4-methoxycarbonyloxybutyl, 4-ethyl Carbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfaylpropyl, 4-sulfaylbutyl, and the like. Among these, particularly preferred R ₁ , R ₂ and R ₄ are independently hydrogen, methyl or ethyl.

그룹의 예로는

및

가 있다. 이들 R₃중, 바람직한 것은 아세틸 또는 프로피오닐이다.Examples of acyl represented by R ₃ include acetyl, propionyl, butyryl, isobutyryl, valeryl and benzoyl, and the structural formula represented by R ₃

Examples of groups

And

There is. Of these R ₃ , preferred are acetyl or propionyl.

The phenylene group represented by A includes, for example, one or two substituents selected from methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo and unsubstituted phenylene groups, and the naphthalene group represented by A Includes naphthalene and sulfo-substituted naphthalene. Preferred examples of phenylene and naphthylene groups are as follows:

에 결합되어 있다.)(In the above general formula, the coupling sites marked with an asterisk are groups

Is bound to.)

In the group represented by Z, Y in -SC ₂ CH ₂ CH ₂ Y represents a group that can be separated by the action of alkylli, e.g. sulfate ester, thiosulfate ester, phosphate ester and acetic ester group, and halogen atom Include. Of these, particularly preferred Z are -SO ₂ CH = CH ₂ and -SO ₂ CH ₂ CH ₂ OSO ₃ H.

An example of a group marked B is as follows.

에 결합되어 있다.(In the above formula, the bond marked with an asterisk is a group

Is coupled to

In the lower alkoxy group represented by X, compounds containing 1 to 4 carbon atoms are preferable, for example, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-part Oxy and the like. Especially preferred are methoxy, ethoxy, n-propoxy, iso-propoxy, and β-ethoxyethoxy.

Preferred examples of the phenoxy group also denoted by X are groups unsubstituted or substituted with one or two groups selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, nitro, sulfo, carboxyl and chlorine. Phenoxy, 3- or 4-sulfophenoxy, 2,4- or 3,5-disulfofeneoxy and the like are particularly preferred.

에 있어서, R₇및 R₈으로 표시한 바람직한 저급 알킬그룹은 탄소원자 1 내지 4개를 함유하는 화합물이며, C₁-C₄알콕시, 설포, 카복실, 하이드록시, 염소, 페닐 및 설페이트중에서 선택된 하나 또는 두개의 그룹으로 치환되거나 비치환된다. 메틸, 에틸, n-프로필, 이소-프로필, n-부틸, 이소-부틸, 2급-부틸, 2-하이드록시에틸, 2-설파토에틸, 2-설포에틸, 2-메톡시에틸 및 2-카복시에틸이 특히 바람직한 그룹이다.Group marked with an X

In the above, preferred lower alkyl groups represented by R ₇ and R ₈ are compounds containing 1 to 4 carbon atoms and are selected from C ₁ -C ₄ alkoxy, sulfo, carboxyl, hydroxy, chlorine, phenyl and sulfate Or substituted or unsubstituted with two groups. Methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, secondary-butyl, 2-hydroxyethyl, 2-sulphatoethyl, 2-sulfoethyl, 2-methoxyethyl and 2- Carboxyethyl is a particularly preferred group.

Preferred phenyl groups represented by R ₇ and R ₈ are groups unsubstituted or substituted with one or two groups selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfo, carboxyl and chlorine. Of these, phenyl, 2-, 3- or 4-sulfophenyl, 2-, 3- or 4-carboxyphenyl, 3,4- 3,5- or 3,6-disulfophenyl and the like are particularly preferable.

Preferred naphthyl groups represented by X are groups unsubstituted or substituted with one to three groups selected from among hydroxyl, carboxyl, sulfo C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and chlorine. Among these, 2-, 3-, 4-, 5-, 6-, 7- or 8-sulfo-1-, naphthyl, 1-, 5-, 6-, 7- or 8-sulfo-2-naph Teal, 2,4-, 5,7-, 6,8-, 4,8-, 4,7-, 3,8-, 4,6-, 3,7-, or 3,6-disulfo- 2-naphthyl, 4,6,8-, 2,4,7- or 3,6,8-trisulfo-1-naphthyl, 1,5,7-, 4,6,8- or 3,6 , 8-trisulfo-2-naphthyl and the like are particularly preferred.

Preferred benzyl groups represented by R ₇ and R ₈ are groups unsubstituted or substituted with one or two groups selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfo and chlorine. Of these, benzyl and 2-, 3- or 4-sulfobenzyl are particularly preferred.

The monoazo compound of the present invention of general formula (I) may be in the form of a salt of a free acid or an alkali or a salt of an alkaline earth metal. Of these, sodium salts and potassium salts are preferred.

In general formula (I), the monoazo compound of the said general formula (I ') which has a chlorine or a bromine atom as X can be manufactured, for example by the following method.

The first condensation of either the diamine compound of formula (II) or the aromatic amine of formula (III) with cyanuric acid chloride or cyanuric acid fluoride is carried out together with the residual compound of (III) or (II). 2 Condensate.

(Ⅱ)

(Ⅱ)

Wherein R ₂ and B are as defined above. The first and second condensation reactions are each -10 to 50 ° C, preferably 0 to 30 ° C and a pH of 1 to 10, preferably 2 to 7, and a temperature of 0 to 70 ° C and 3 to 7 May be carried out in an aqueous medium at the desired pH of.

The resulting amine compound of formula (IV) is diazotized at a temperature of -10 to 20 ° C. in a conventional manner, and then -10 to 50 ° C., adjusting the pH within the range of 1 to 7, preferably 1 to 5, Preferably, the desired monoazo compound (I ') may be prepared by coupling with a naphthol compound of formula (V) at a temperature of 0 to 30 ° C.

Alternatively, the monoazo compound of general formula (I ') can also be prepared by the following method.

The diamine compound (II) or the nitro compound of the following general formula (VII) is diazotized at a temperature of -10 to 20 DEG C by a conventional method, while adjusting the pH to 1 to 7, preferably 1 to 5, and then -10 to Coupling with naphthol compound (V) at a temperature of 50 ° C:

H ₂ NB-NO ₂ (Ⅳ)

Wherein B is as described above. The resulting compound obtained using nitro compound (VII) is then reduced at a temperature of 40-100 ° C. in the presence of sodium sulfide. According to any of the above methods, a monoazo naphthol compound of the general formula can be produced.

Subsequently, either the monoazo naphthol compound (i) or the aromatic amine compound (III) is adjusted to -10 to 50 ° C, preferably 0 to 30 ° C, with the pH being adjusted in the range of 1 to 10, preferably 2 to 7. First condensation with cyanurate or cyanuric acid fluoride at a temperature of 0 to 70 ° C., preferably 10 to 50 ° C., while adjusting the pH to a range of 2 to 9, preferably 3 to 6 The second condensation is carried out with the residual compound of (III) or (iii) to obtain the desired monoazo compound (I ').

의 그룹을 갖는 일반식(Ⅰ")의 모노아조 화합물을 다음 방법으로 제조할 수 있다. 전술한 방법으로 제조할 수 있는 모노아조 화합물(Ⅰ')을 pH 2 내지 9, 바람직하게는 3 내지 7로 조절하면서 50 내지 100℃, 바람직하게는 70 내지 100℃의 온도에서 수성매질중에서 X₂가 전술한 바와같은 일반식 H-X₂(Ⅷ)의 화합물과 축합시킨다.Lower alkoxy or unsubstituted or substituted phenoxy groups R ₇ and R ₈ as X in formula (I) are as defined above

The monoazo compound of general formula (I ") having the group of can be prepared by the following method. The monoazo compound (I ') which can be prepared by the above-mentioned method is pH 2 to 9, preferably 3 to 7 X ₂ is condensed with a compound of the general formula HX ₂ (VII) as described above in an aqueous medium at a temperature of from 50 to 100 ° C., preferably from 70 to 100 ° C., with control.

Alternatively, the monoazo naphthol compound (v) or any one of the compounds (v) is first condensed with cyanurate or cyanuric acid fluoride, and then the compound (v) or the residual compound of (v) and the second Condensation. The first condensation reaction may be performed at a temperature of −10 to 50 ° C., preferably 0 to 30 ° C. while adjusting the pH to 1 to 10, preferably 4 to 7, and the second condensation reaction may be performed at a pH of 2 to 10, preferably 4 to 9, it may be carried out at a temperature of 10 to 70 ℃, preferably 20 to 50 ℃. The resulting compound is then condensed with the aromatic amine compound (II) at a temperature of 50 to 100 ° C., preferably 80 to 100 ° C., while adjusting the pH to 2 to 9, preferably 3 to 7.

Therefore, the desired monoazo compound of general formula (I ") can be manufactured.

Particularly preferred examples of naphthol compound (V) useful for the preparation of monoazo compound (I) are as follows:

Compounds that can be used to prepare monoazo compound (I) include ammonia, aromatic and aliphatic amines, lower alcohols and substituted phenols.

Examples of aromatic amines include 1-aminobenzene, 1-amino-2-, 3- or 4-methylbenzene, 1-amino-2,4-, 2,5-, 3,4- or 3,5-dimethylbenzene , 1-amino-2-, 3- or 4-ethylbenzene, 1-amino-2-, 3- or 4-methoxybenzene, 1-amino-4-ethoxybenzene, 1-amino-2-, 3 Or 4-chloro-benzene, 3- or 4-amino-phenylmethane sulfonic acid, 2-, 3- or 4-aminobenzene sulfonic acid, 3-methylamino-benzenesulfonic acid, 4-methylamino benzenesulfonic acid, 4-ethylaminobenzenesulfonic acid, 5-aminobenzene-1,3-disulfonic acid, 2-aminobenzene-1,4-disulfonic acid, 4-aminobenzene-1,3-disulfonic acid, 2-, 3- or 4-aminobenzoic acid, 5-aminobenzene-1,3-dicarboxylic acid, 5-amino-2-hydroxybenzenesulfonic acid, 4-amino-2-hydroxy benzenesulfonic acid, 5-amino-2-ethoxybenzene Sulfonic acid, N-methylaminobenzene, N-ethylaminobenzene, 1-ethylamino-3- or 4-methylbenzene, 1-ethylamino-4-chlorobenzene, 1-ethylamino-3- or 4-methylbenzene , 1- (2- Idroxyethyl) amino-3-methylbenzene, 3- or 4-methylaminobenzoic acid, 3- or 4-methylaminobenzenesulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 4-aminonaphthalene-1-sulfonic acid , 5-aminonaphthalene-1-sulfonic acid, 6-aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-1-sulfonic acid, 1-aminonaphthalene-2-sulfonic acid , 4-aminonaphthalene-2-sulfonic acid, 5-aminonaphthalene-2-sulfonic acid, 6-aminonaphthalene-2-sulfonic acid, 7-aminonaphthalene-2-sulfonic acid, 7-methylaminonaphthalene-2-sulfur Phonic acid, 7-ethylaminonaphthalene-2-sulfonic acid, 7-butylaminonaphthalene-2-sulfonic acid, 7-isobutylaminonaphthalene-2-sulfonic acid, 8-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene -1,3-disulfonic acid, 5-aminonaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid, 8-aminonaphthalene-1 , 3-disulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid , 3-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,6-disulfonic acid, 8-aminonaphthalene-1,6-disulfonic acid, 4 -Aminonaphthalene-1,7-disulfonic acid, 3-aminonaphthalene-2,6-disulfonic acid, 4-aminonaphthalene-2,6-disulfonic acid, 3-aminonaphthalene-2,7-disulfonic acid, 4-amino Naphthalene-2,7-disulfonic acid, 6-aminonaphthalene-1,3,6-trisulfonic acid, 7-aminonaphthalene-1,3,5-trisulfonic acid, 4-aminonaphthalene-1,3,6- Trisulfonic acid, 7-aminonaphthalene-1,3,6-trisulfonic acid, 8-aminonaphthalene-1,3,6-trisulfonic acid, 4-aminonaphthalene-1,3,7-trisulfonic acid and the like have.

Examples of aliphatic amines include methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, secondary-butylamine, dimethylamine, diethylamine, methylethylamine, allylamine , 2-chloroethylamine, 2-methoxyethylamine, 2-aminoethanol, 2-methylaminoethanol, bis- (2-hydroxyethyl) -amine, 2-acetylaminoethylamine, 1-amino-2- Propanol, 3-methoxy-propylamine, 1-amino-3-dimethylaminopropane, 2-aminoethanesulfonic acid, aminomethanesulfonic acid, 2-methylaminomethanesulfonic acid, 3-amino-1-propanesulfonic acid, 2-sulfatoethylamine, aminoacetic acid, methylaminoacetic acid, 3-aminocaproic acid, benzylamine, 2-, 3- or 4-chlorobenzylamine, 4-methylbenzylamine, N-methylbenzylamine, 2- , 3- or 4-sulfobenzylamine, 2-phenylethylamine, 1-phenylethylamine, 1-phenyl-2-propylamine and the like.

Examples of feed alcohols include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol and the like.

Examples of substituted phenols include 3- or 4-sulfophenol, 2,4- or 3,5-disulfophenol, 2-nitro-4-sulfophenol, 2-chloro-4-sulfophenol and the like.

Particularly preferred of these compounds exemplified by the compounds of formula (VII) include aniline, N-methylaminobenzene, N-ethylaminobenzene, 3-aminobenzenesulfonic acid, 3-methylaminobenzenesulfonic acid, 3 -Ethylaminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 4-methylaminobenzenesulfonic acid, 4-ethylaminobenzenesulfonic acid, pseudo- or di-ethanolamine, and the like.

Examples of nitro compounds are as follows:

Monoazo compounds (I) according to the invention are useful for dyeing or printing materials which are fiber-reactive, contain hydroxyl groups and contain amide groups. This material is advantageously present in the form of fibers, including unblended or blended fiber spuns.

The hydroxyl group-containing material is a natural or synthetic hydroxyl group-containing material such as cellulose fiber material, cellulose-containing fiber material, regeneration products thereof and polyvinyl alcohol. Examples of cellulose fiber materials are vegetable fibers such as cotton and flax, hemp, jute and ramie fibers. Examples of regenerated cellulose fibers are viscose staples and filament viscose. Examples of cellulose-containing fiber materials are blended fiber materials such as cellulose / polyester, cellulose / wool, cellulose / acrylic, and the like.

Amide group-containing materials are synthetic or natural polyamides and polyurethanes. Examples of especially fibrous form materials are wool and other animal fur, silk, leather, polyamide-6,6-polyamide-6, polyamide-11 and polyamide-4.

The dyeing is carried out by selecting an appropriate method from the conventional methods according to the physical and chemical properties of the fiber material.

For example, the cellulose fiber material can be dyed using the present compound by the adsorption salt method, the padding salt method including the cold batch salt method or the printing method.

The adsorption salt method can be carried out at relatively low temperatures in the presence of acid binders such as sodium carbonate, sodium phosphate, sodium hydroxide and the like, optionally using neutral salts such as sodium sulfate, sodium chloride, etc., optionally with dissolution aids, penetrants or leveling agents. Neutral salt is added to the dye bath when or before the batch temperature has reached the desired degree for dyeing to promote the adsorption of the dye. Neutral salts can also be added in portions.

The padding salt method can be carried out by padding the fibrous material at ambient or elevated temperature and dye-fixing the material after drying by steam treatment or dry-heating.

The printing method can be carried out by a one-phase or two-phase method. The one-phase printing method is carried out by printing the fiber material with a printing paste containing an acid binder such as sodium hydrogen carbonate and steaming at a temperature of 100 ° to 160 ° C.

Two-phase printing is performed by printing the fiber material with a neutral or weakly acid printing paste, passing the foreign material through a hot alkaline bath containing the electrolyte or by excessively padding the material with an alkaline padding liquid containing the electrolyte, This is followed by steam treatment or dry-heat treatment.

For the production of printing pastes, pastes or emulsifiers such as sodium alginate, starch ethers and the like may optionally be used in combination with conventional auxiliaries such as urea and / or dispersants.

Acid binders useful for immobilizing the compounds of the present invention on cellulose fibers include water-soluble basic salts consisting of alkali or alkaline earth metals, and inorganic or organic acids, or compounds capable of liberating alkali under heated conditions. Preferred are alkali metal hydroxides and alkali metal salts of weak or medium strength inorganic or organic acids. Especially preferred are sodium salts and potassium. Examples thereof include sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium silicate, sodium trichloro acetate and the like.

Staining of natural or synthetic polyamides and polyurethane fiber materials can be carried out by adjusting the pH value, carrying out the adsorption in an acid or weak acid bath and then making the bath neutral or in some cases alkaline to perform the fixation. The dyeing temperature range is usually 60 to 120 ℃. To achieve the leveling salt, conventional leveling agents such as condensation products of cyanuric acid chloride with 3-fold molar aminobenzene-sulfonic acid or amino naphthalene sulfonic acid, or addition products of stearylamine with ethylenoxide, and the like can be used.

The monoazo compound (I) of the present invention can be characterized by its excellent dyeing ability in dyeing and printing fibrous materials, in particular cellulose fibrous materials. For example, the compound may be of daylight fastness, sweat-fastness, sweat-fastness, wash fastness, peroxide-wash fastness, chlorine fastness, chlorine bleaching fastness, acid-hydrolysis fastness, alkali fastness It is possible to provide dyeings having excellent wear fastness and iron fastness, especially formalin fastness and popmalin fastness to daylight fastness. The monoazo compound (I) also shows high adsorption and fixation rates, as well as good build-up, leveling and washing power and high solubility. In addition, since the monoazo compound (I) is hardly affected by the change in the dyeing temperature, the type of alkali agent, the amount of the inorganic salt to be used and the ratio of the dye bath, the dyeing product of a certain quality can obtain excellent regeneration. In addition, in the cold batch salt method, the monoazo compound (I) has excellent alkali stability, including build-up characteristics and insensitivity to hydrolysis by an alkaline agent, and two fixing processes are performed at relatively low temperatures and 25 ° C, respectively. In all cases, the same characteristics can be found in which the difference in dyeing density and color tone of the dyed product cannot be found.

The invention is explained in more detail with reference to the following examples, which are illustrative only and not limiting. In the examples parts and percentages are by weight.

Example 1

2,4-diamino benzenesulfonic acid (18.8 parts) was added to a suspension prepared by dispersing cyanuric acid chloride (18.5 parts) in ice water (250 parts), and the mixture was adjusted to pH 2-4 with 20% aqueous solution of sodium carbonate. While stirring for 0 to 5 ℃ 6 hours to carry out the first condensation reaction.

1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts) was added to the resulting reaction mixture, and the mixture was stirred at 10 to 20 ° C. for 7 hours while adjusting the mixture to a pH of 4 to 6 with 20% aqueous solution of sodium carbonate. To allow the second condensation reaction to occur.

Subsequently, concentrated hydrochloric acid (25.3 parts) is added to the reaction mixture, followed by 35% aqueous solution of sodium nitrite (21.7 parts) to allow diazotization reaction. If excess nitrous acid has been decomposed, 7-methylamino-1-naphthol-3-sulfonic acid (25.3 parts) is added and the resulting mixture is adjusted to pH in the range of pH 1-3 with 20% aqueous solution of sodium carbonate. The coupling reaction is carried out by stirring overnight at 5 ° C. Next, the reaction mixture is heated to 40 ° C. and adjusted to pH 4-6, followed by salting with sodium chloride (20 parts). The resulting crystals were separated on a filter paper, washed and dried at 60 ° C. to obtain the monoazo compound of formula (I) in free acid form:

[Examples 2 to 62]

The method of Example 1 was repeated, except that instead of 7-methylamino-1-naphthol-3-sulfonic acid, each of the naphthol compounds of formula (V) shown in column 2 of the following table was used, respectively; Instead of 2,4-diaminobenzene sulfonic acid, diamine compounds of formula (II) shown in column 3 are used, respectively; Using cyanuric acid chloride or cyanuric acid fluoride described in column 4 (C and F in column 4 respectively represent cyanuric acid chloride and cyanuric acid fluoride); Instead of 1-aminobenzene-3-β-sulfatoethylsulfone, each of the aromatic amine compounds of formula (III) shown in column 5 is used to obtain corresponding monoazo compounds. Structural formulas used in Examples 23 and 34

Compounds of can be prepared by acetylating the amino group of 2,4-diaminobenzenesulfonic acid, followed by subsequent chlorination and hydrolysis.

Example 63

A solution containing 35% aqueous solution of sodium nitrite (21.7 parts) and 2-methoxy-4-nitroaniline-5-sulfonic acid (24.8 parts) in water (150 parts) was adjusted to a temperature of 0 ° to 5 ° C. It is introduced into a solution containing ice water (300 parts) and concentrated hydrochloric acid (35.5 parts), and the mixture is diazotized by stirring at the same temperature for 1 hour.

Subsequently, when excess nitrous acid is decomposed, 7-ethylamino-1-naphthol-3-sulfonic acid (26.7 parts) is added to the reaction mixture, and the mixture is adjusted to pH in the range of 1 to 3 using 20% aqueous solution of sodium carbonate. While controlling, the mixture is stirred for 2 hours at 0 ° C to 5 ° C. The reaction mixture is then adjusted to pH 8-10, mixed with sodium sulfide (10.7 parts), heated to 60 ° C. and stirred at the same temperature for 3 hours to effect the reduction reaction. The reaction mixture is then mixed with sodium chloride (40 parts) to precipitate crystals which are then collected on a filter paper and washed. The resulting wet cake is dissolved in water (400 parts). The solution is mixed with cyanuric acid chloride (16.7 parts) and the mixture is stirred at 0 ° to 10 ° C. for 5 hours while adjusting the pH to 2-3 with 20% aqueous solution of sodium carbonate to allow the first condensation reaction. 2-Aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid (37 parts) was added to the reaction mixture, and the mixture was heated to 20 DEG C while adjusting the pH to 4-5 using a 20% aqueous solution of sodium carbonate. The second condensation reaction is carried out by stirring at 30 ° C. for 15 hours. Next, the reaction mixture was mixed with sodium chloride (40 parts) to precipitate the crystals, collected on a filter paper, washed and dried at 60 ° C. to give the desired monoazo compound of the formula (63) in the form of a free acid. :

[Examples 64 to 86]

The method of Example 63 was repeated, with the exception of 7-ethylamino-1-naphthol-3-sulfonic acid, using the naphthol compounds of formula (V) shown in the second column of the following table, respectively, and 2-methoxy Instead of 4-nitroaniline-5-sulfonic acid, the compounds of formula (VII) shown in column 3 are used, respectively, and cyanuric chloride or cyanuric fluoride described in column 4, wherein Cl and F are cyanur Acid chloride and cyanuric acid fluoride], and instead of 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid, using an aromatic amine compound of formula (III) shown in column 5 , To obtain the corresponding monoazo compound.

Example 87

The monoazo compound of the following structural formula (98.7 parts) obtained in Example 2 in the free acid form is dissolved in water (500 parts), and 3-aminobenzenesulfonic acid (34.6 parts) is added to the resulting solution.

The mixture is heated to 80 ° to 85 ° C. with 20% aqueous sodium carbonate solution adjusting the pH to 4-6 and stirred at this temperature and pH for 7 hours. The reaction mixture is then mixed with sodium chloride (45 parts) to precipitate crystals. The resulting crystals are collected on filter paper, washed and dried at 60 ° C. to give the monoazo compound of formula (87) in free acid form.

[Examples 88 to 119]

The method of Example 87 was repeated but using each of the monoazo compounds described in the table below instead of the monoazo compounds obtained in Example 2 (the monoazo compounds used are described in column 2 of the table below, each run And each of the compounds of formula IV in place of 3-amino-benzenesulfonic acid to give the corresponding desired monoazo compound.

Example 120

35% aqueous solution of sodium nitrite (21.7 parts) 2-amino-5-aminomethylnaphthalene-1-sulfonic acid (27.4 parts) and concentrated hydrochloric acid (35.5 parts) in ice water (300 parts) while adjusting the temperature to 0-5 ° C Is added to the solution. The resulting mixture is stirred at this temperature for 1 hour to carry out the diazotization reaction. Subsequently, after decomposing the excess nitrous acid, 7-ethylamino-1-naphthol-3-sulfonic acid (26.7 parts) was added and the mixture was adjusted to pH 3 to 5 using 20% aqueous sodium carbonate solution, and the mixture was allowed to react for 12 hours. A monoazo compound-containing solution is obtained by carrying out the coupling reaction by stirring at 0-5 [deg.] C.

Meanwhile, water (30 parts) and sodium carbonate (8.4 parts) are added to methanol (300 parts), and cyanuric acid chloride (18.5 parts) is added thereto. The mixture is stirred at 0-10 ° C. for 30 minutes. The resulting reaction mixture is added to the monoazo compound-containing solution and the mixture is stirred at 30 ° to 40 ° C. for 6 hours, with the pH adjusted to 7-8 using 20% aqueous sodium carbonate solution.

1-ethylaminobenzene-4-β-sulfatoethylsulfone (30.9 parts) was added to the reaction mixture, and the reaction mixture was heated to 80 to 90 DEG C while adjusting the pH to 3-5 using 20% aqueous sodium carbonate solution. Stir at this temperature and pH for 15 hours. The reaction mixture is then cooled to 40 ° C. and mixed with sodium chloride (40 parts) to precipitate crystals. The resulting crystals are collected on filter paper, washed and dried at 60 ° C. to give the monoazo compound of formula 120 in free acid form.

[Examples 121 to 141]

The method of Example 120 was repeated, with the exception that 2-amino-5-aminomethylnaphthylene-1-sulfonic acid was used instead of each of the diamine compounds of formula (II) described in column 3 of the following table, and 7-ethylamino Instead of -1-naphthol-3-sulfonic acid, each of the naphthol compounds of formula (V) shown in column 2 of the table below is used, and each of the compounds of formula (VII) shown in column 4 of the table below Instead of 1-ethylaminobenzene-4-β-sulfatoethylsulfone, each of the aromatic amine compounds of formula (III) shown in column 5 of the following table is used to obtain the corresponding desired monoazo compounds.

Example 142

The method of Example 1 was repeated, except 2-methylamino-8-hydroxynaphthalene-3,6-disulfonic acid (33.3 parts) instead of 7-methyl amino-1-naphthol-3-sulfonic acid (25.3 parts). To obtain the desired monoazo compound of formula (142) in free acid form.

[Examples 143 to 196]

The method of Example 1 was repeated, with the exception that 7-methylamino-1-naphthol-3-sulfonic acid was used instead of each of the naphthol compounds of formula (V) shown in column 2 of the table below and 1,3-diamino Instead of benzene-4-sulfonic acid, each of the diamine compounds of the formula (II) shown in column 3 of the table below is used, and column 4 (where Cl and F represent chloride cyanuric chloride and cyanuric acid fluoride, respectively) Using the cyanuric acid chlorides or cyanuric acid fluorides shown in Fig. 3 and using each of the aromatic amine compounds of formula (III) shown in column 5 instead of 1-aminobenzene-3-β-sulphotoethylsulfone, The desired monoazo compound is obtained.

Example 197

The method of Example 63 was repeated, except 2-methylamino-8-hydroxy naphthalene-3,6-disulfonic acid (33.3 parts) instead of 7-ethylamino-1-naphthol-3-sulfonic acid (26.7 parts). To obtain the monoazo compound of formula (197) in free acid form.

[Examples 198 to 233]

The method of Example 63 was repeated, with the exception of 7-ethylamino-1-naphthol-3-sulfonic acid, using each of the naphthol compounds of formula (V) shown in column 2 of the table below and using 2-methoxy-4 Instead of nitroaniline-5-sulfonic acid, each of the nitro compounds of the structural formula shown in column 3 is used, and in column 4, where Cl and F represent cyanuric chloride and cyanuric acid fluoride, respectively. Using the described cyanuric acid chlorides or cyanuric acid fluorides and using each of the aromatic amine compounds shown in column 5 instead of 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid, the corresponding purpose Obtain a monoazo compound.

Example 234

The monoazo compound (92.7 parts) of formula (186) in the form of the free acid obtained in Example 186 is dissolved in water (500 parts) and 3-aminobenzenesulfonic acid (34.6 parts) is added to this solution.

The mixture is heated to 80-85 ° C. while adjusting the pH to a range of 4-6 using 20% aqueous sodium carbonate solution and then stirred for 7 hours at the temperature and pH described above. The reaction mixture was then mixed with sodium chloride (45 parts) to precipitate crystals which were collected on a filter paper, washed and washed at 60 ° C. Drying affords the monoazo compound of formula (234) in free acid form.

[Examples 235 to 274]

The method of Example 234 was repeated, with the exception of the monoazo compounds obtained in Example 186, with each monoazo compound shown in column 2 of the following table (the monoazo compound used is represented by each example number) Each compound shown in column 3 is used in place of 3-amino-benzenesulfonic acid to yield the corresponding desired monoazo compound.

Example 275

The procedure of Example 120 was repeated except that 2-methylamino-8-hydroxynaphthalene-3,6-disulfonic acid (33.3 parts) was replaced with 7-ethylamino-1-naphthol-3-sulfonic acid (26.7 parts). Used instead to give the monoazo compound of formula (275) in free acid form.

[Examples 276 to 293]

The method of Example 120 was repeated except that each diamine compound of formula (II) shown in column 3 of the table below was used in place of 2-amino-5-aminomethyl niphthalene-1-sulfonic acid and shown in column 2 Each naphthol compound of formula (V) is used in place of 7-ethylamino-1-naphthol-3-sulfonic acid, and each compound of formula (VII) shown in column 4 is used in place of methanol, and The aromatic amine compound of formula III shown is used in place of 1-ethylaminobenzene-4-β-sulfatoethylsulfone to obtain the corresponding desired monoazo compound.

Dyeing Example 1

Monoazo compounds (1) and (142) (0.3 parts each) obtained in Examples 1 and 142 were dissolved in water (200 parts), and sodium sulfate (20 parts) and cotton (10 parts) were added. The bath is heated to 50 ° C. and then sodium carbonate (4 parts) is added. Staining is continued at this temperature for 1 hour. The cotton is then washed with water and soaped to give a dark red dyeing product. Both dyeing products have been found to have good fastness, in particular formalin fastness, daylight fastness and sweat fastness, and the two monoazo compounds have been found to have good build-up properties.

Dyeing Example 2

The monoazo compounds 63 and 197 (0.3 parts each) obtained in Examples 63 and 197 were dissolved in water (150 parts), and sodium sulfate (30 parts) and cotton (10 parts) were added. The bath is heated to 60 ° C. After 20 minutes sodium carbonate (4 parts) is added. Staining is continued for 1 hour at ionic degrees. The cotton is washed with water and soaped to give a dark red dyed product with good build-up properties and good fastness, in particular formalin fastness, daylight fastness and sweat fastness.

Dyeing Example 3

Each of the monoazo compounds (0.3 parts) obtained in Examples 1 to 86 and 142 to 233 (0.3 parts) is dissolved in water (300 parts), to which sodium sulfate (30 parts) and cotton (10) are added. The bath is heated to 60 ° C. After 20 minutes, sodium carbonate (5 parts) is added thereto and the dyeing is continued at this temperature for 1 hour. The cotton is washed with water and soaped to give a dark red dyed product with good build-up properties and good fastness, in particular formalin fastness, daylight fastness and sweat fastness.

Dyeing Example 4

Each of the monoazo compounds obtained in Examples 87 to 141 and 234 to 293 (0.3 parts) was dissolved in water (200 parts), and sodium sulfate (30 parts) and cotton (10 parts) were added thereto. The bath is heated to 50 ° C. After 30 minutes, trisodium phosphate (4 parts) is added thereto, and the dyeing is continued for 1 hour at this temperature. The cotton is then washed and soaped as well to obtain a dark red dyed product with good build-up properties and good fastness, in particular formalin fastness, daylight fastness and sweat fastness.

Dyeing Example 5

Composition part of the color paste

In Examples 1 to 86 and 142 to 233

Each of the obtained monoazo compounds 5

Urea 5

Sodium Alginate (5%), Thickening Agent 50

Hot water 25

Sodium bicarbonate 2

Remaining water (water) 13

The wide cotton cloth polished is printed with color paste having the composition described above, then pre-dried, steamed at 100 ° C. for 5 minutes, washed with warm water, soaped, washed again with warm water and dried. In this way, a dark red printing product is obtained which has high fastness, in particular formalin fastness, daylight fastness and sweat fastness, with high high rate and good build-up properties.

Dyeing Example 6

Composition part of the color paste

In Examples 87-141 and 234-293

Each of the obtained monoazo compounds 4

Urea 5

Sodium Alginate (5%), Thickening Agent 50

Hot water 25

Sodium bicarbonate 2

Remaining water (water) 14

Using the color paste of the above composition, a similar procedure to that described in dyeing example 6 was repeated except that steam was drawn at 120 ° C. to obtain a dyeing product as in dyeing example 5.

Dyeing Example 7

Each of the monoazo compounds obtained in Examples 1 to 86 and 142 to 233 (25 parts) is dissolved in coma and the solution is cooled to 25 ° C. To this was added 32.5% aqueous sodium hydroxide solution (5.5 parts) and 50 ° Be 'water glass, and water was added to make 1000 parts in total at 20 ° C. to obtain a padding liquid. Immediately, the cotton cloth is padded with padding liquid and then placed, and the fabric is tightly wrapped with a pulley polyethylene film and left in a room at 20 ° C. The method is repeated to obtain a padded cotton cloth, which is then tightly wrapped with polyethylene film and left in a room at 5 ° C.

Both are left to stand for 20 hours and then washed with cold water and then hot water, soaped hard to boil, washed with cold water and dried.

Little difference in color tone and darkness was observed between the dyed products obtained after standing at 5 ° C. and 20 ° C. for 20 hours, respectively. In this cold batch salt method, each monoazo compound was found to have excellent build-up properties.

Dyeing Example 8

Using the monoazo compounds obtained in Examples 87-141 and 234-293, dyeing Example 7 is repeated. As a result, a result similar to that of dyeing example 7 is obtained.

Dyeing Example 9

The monoazo compounds (25 parts each) obtained in Examples 1 to 86 and 142 to 233 are dissolved in warm water and the solution is cooled to 25 ° C. To this solution is added 32.5% aqueous sodium hydroxide solution (10 parts) and anhydrous sodium sulfate (30 parts), followed by adding water to make 1000 parts at 25 ° C. Immediately thereafter, the viscose rayon fabric is padded with padding liquid. The fabric is placed and tightly wrapped with polyethylene film and left in a room at 20 ° C.

The method is repeated to obtain a padded fabric, placed and placed in a room at 5 ° C. tightly wrapped with polyethylene film.

Both are left for 20 hours, washed with cold water and then with hot water, washed with soap, soaped, then washed with cold water and dried to obtain the respective dyed product. Little difference in color tone and color was observed between the dye products obtained after standing at 5 ° C. and 20 ° C. for 20 hours, respectively.

Dyeing Example 10

Using the monoazo compounds obtained in Examples 87 to 141 and 234 to 293, the same procedure as in the dyeing example 9 was carried out to give results similar to those of the above examples.

Dyeing Example 11

Dyeing Example 3 was repeated with the exception that the amount of sodium carbonate was used in 3 parts instead of 5 parts to obtain results similar to those of dyeing example 3.

Dyeing Example 12

Dyeing Example 3 is repeated and dyeing is continued at 60 ° C. and 70 ° C. instead of only 50 ° C., to give results similar to those of Dyeing Example 3.

Dyeing Example 13

Repeating Dyeing Example 3, except that the amount of sodium sulfate is used in 15 parts instead of 30 parts, to obtain a result similar to that of Dyeing Example 3.

Dyeing Example 14

Repeating Dyeing Example 4, using water and sodium sulfate, 150 parts and 23 parts instead of 200 parts and 30 parts, respectively, to obtain a result similar to that of Dyeing Example 4.

Claims (20)

A diazonium salt of the amine compound of formula (IV) is reacted with a naphthol compound of formula (V) to prepare a monoazo compound of formula (I ') in free acid form.

Wherein R ₁ and R ₂ each independently represent hydrogen or unsubstituted or substituted lower alkyl; R ₃ is unsubstituted or substituted lower alkyl, acyl or structural formula

Represents a group of; R ₄ represents hydrogen or unsubstituted or substituted lower alkyl; R ₅ represents hydrogen or sulfo; B is a general formula

Group or structural formula

R ₆ represents hydrogen, chlorine, sulfo, carboxy, methyl, methoxy or ethoxy, and X ₁ represents chlorine or fluorine; A represents an unsubstituted or substituted phenylene or naphthylene group; Z is -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ represents a group of CH ₂ Y, where, Y is a group which can be removed by the action of an alkali. A compound according to claim 1, wherein R ₁ and R ₂ each independently represent hydrogen or methyl or ethyl, and A is unsubstituted or selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo Or a monoazo compound of formula (I ′) representing phenylene substituted by two substituents, or naphthylene unsubstituted or substituted by one sulfo. The compound of claim 1, wherein Z is —SO ₂ CH═CH ₂ , —SO ₂ CH ₂ CH ₂ OSO ₃ H, —SO ₂ CH ₂ CH ₂ SSO ₃ H, —SO ₂ CH ₂ CH ₂ OPO ₃ H ₂ or A method for producing a monoazo compound of general formula (I '), -SO ₂ CH ₂ CH ₂ OCOH ₃ . The compound of claim 1 wherein B is

(Where the asterisk is a group

To a monoazo compound of the general formula (I '). The process according to claim 1, wherein the monoazo compound of general formula (') is a compound of the following general formula in free acid form.

In which R ₅ represents hydrogen or sulfo; R ₁₀ represents hydrogen, methyl or ethyl; R ₁₁ represents hydrogen, chlorine or sulfo; R ₁₂ represents methyl, ethyl, acetyl or propionyl; R ₁₃ represents hydrogen, methyl or ethyl; Z ₁ represents a CH ₂ = CH ₂ or -SO _{-SO 2 CH 2 CH 2 OSO 3} H. The process according to claim 1, wherein the monoazo compound of the general formula (I ') is a compound of the following general formula in free acid form.

Wherein R ₅ represents hydrogen or sulfo; R ₁₀ represents hydrogen, methyl, or ethyl; R ₁₁ represents hydrogen, chlorine or sulfo; R ₁₂ represents methyl, ethyl acetyl or propionyl; R ₁₃ represents hydrogen, methyl or ethyl; R ₁₄ represents hydrogen or sulfo; Z ₁ represents a CH ₂ = CH ₂ or -SO _{-SO 2 CH 2 CH 2 OSO 3} H. Either the aromatic amine compound of general formula (III) or the monoazo naphthol compound of general formula (III) is reacted with cyanuric acid chloride or cyanuric acid fluoride, and then general formula (III) and general formula (VII) compound A method for producing a monoazo compound of the general formula (I ') in free acid form, characterized in that it reacts with the other one not reacted in the above.

Wherein R ₁ and R ₂ each independently represent hydrogen or unsubstituted or substituted lower alkyl; R ₃ is unsubstituted or substituted lower alkyl, acyl or structural formula

Represents a group of; R ₄ represents hydrogen or unsubstituted or substituted lower alkyl; R ₅ represents hydrogen or sulfo; B is a general formula

A group wherein R ₆ is hydrogen, chlorine, sulfo, carboxy, methyl, methoxy or ethoxy; X ₁ represents chlorine or fluorine; A represents an unsubstituted or substituted phenylene or naphthylene group; Z is -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ represents a group of CH ₂ Y, where Y is a group which can be removed by the action of an alkali. 8. A compound according to claim 7, wherein R ₁ and R ₂ each independently represent hydrogen or methyl or ethyl, and A is unsubstituted or selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo or A process for preparing a monoazo compound of formula (I '), which represents phenylene substituted by two substituents or naphthylene unsubstituted or substituted by one sulfo. The compound of claim 7, wherein Z is —SO ₂ CH═CH ₂ , —SO ₂ CH ₂ CH ₂ OSO ₃ H, —SO ₂ CH ₂ CH ₂ SSO ₃ H, —SO ₂ CH ₂ CH ₂ OPO ₃ H ₂ or A method for producing a monoazo compound of general formula (I '), -SO ₂ CH ₂ CH ₂ OCOH ₃ . 8. A compound according to claim 7, wherein B is

(Here, the joining area marked with an asterisk is a group

To a monoazo compound of the general formula (I '). 8. The process of claim 7, wherein the monoazo compound of formula (I ') is a combination of the following general formula in free acid form.

In which R ₅ represents hydrogen or sulfo; R ₁₀ represents hydrogen, methyl or ethyl; R ₁₁ represents hydrogen, chlorine or sulfo; R ₁₂ denotes a methyl, ethyl, acetyl or propionyl, R ₁₃ is a hydrogen, methyl or ethyl, Z ₁ represents a CH ₂ = CH ₂ or -SO _{-SO 2 CH 2 CH 2 OSO 3} H. 8. The process according to claim 7, wherein the monoazo compound of general formula (I ') is a compound of the following general formula in free acid form.

Wherein R ₅ represents hydrogen or sulfo; R ₁₀ represents hydrogen, methyl or ethyl; R ₁₁ represents hydrogen, chlorine or sulfo; R ₁₂ represents methyl, ethyl, acetyl or propionyl; R ₁₃ represents hydrogen, methyl or ethyl; R ₁₄ represents hydrogen or sulfo; Z ₁ represents a CH ₂ = CH ₂ or -SO _{-SO 2 CH 2 CH 2 OSO 3} H. A method for producing a monoazo compound of formula (I ″) in free acid form, characterized by reacting a monoazo compound of formula (I ′) with a compound of formula (VII).

Wherein R ₁ and R ₂ each independently represent hydrogen or unsubstituted or substituted lower alkyl; R ₃ is unsubstituted or substituted lower alkyl, acyl or structural formula

Represents a group of; R ₄ represents hydrogen or unsubstituted or substituted lower alkyl; R ₅ represents hydrogen or sulfo; B is a general formula

Group or structural formula

R ₆ is hydrogen, chlorine, sulfo, carboxy, methyl, methoxy or ethoxy; X ₂ is lower alkoxy, unsubstituted or substituted phenoxy, or general formula

R ₇ and R ₈ are each independently hydrogen or an unsubstituted or substituted lower alkyl, phenyl, naphthyl or benzyl group; A represents an unsubstituted or substituted phenylene or naphthylene group; Z is -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ represents a group of CH ₂ Y, where, Y is a group which can be removed by the action of an alkali; X ₁ represents chlorine or fluorine. 14. A compound according to claim 13, wherein R ₁ and R ₂ each independently represent hydrogen or methyl or ethyl, and A is unsubstituted or selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo or A process for preparing a monoazo compound of general formula (I ″), which represents phenylene substituted by two substituents, or naphthylene unsubstituted or substituted by one sulfo. The method of claim 13, wherein Z is —SO ₂ CH═CH ₂ , —SO ₂ CH ₂ CH ₂ SO ₃ H, —SO ₂ CH ₂ CH ₂ SSO ₃ H, —SO ₂ CH ₂ CH ₂ OPO ₃ H ₂ or -SO ₂ CH ₂ CH ₂ represents OCOH ₃ , X ₂ is a general formula

A group of formulas wherein R _{9 is} hydrogen or methyl or ethyl wherein the monoazo compound of formula (II ") is prepared. The compound of claim 13, wherein B is

(Here, the joining area marked with an asterisk is a group

To a monoazo compound of the general formula (I "). Either the monoazo naphthol compound of formula (VII) or a compound of formula (X) is reacted with cyanuric acid chloride or cyanuric acid fluoride, followed by reaction in compounds of formula (X) and (X) above Reacting with an aromatic amine compound of general formula (III) after reacting with the other one, to prepare a monoazo compound of general formula (I ″) in free acid form.

Wherein R ₁ and R ₂ each independently represent hydrogen or unsubstituted or substituted lower alkyl; R ₃ is unsubstituted or substituted lower alkyl, acyl or structural formula

Represents a group of; R ₄ represents hydrogen or unsubstituted or substituted lower alkyl; R ₅ represents hydrogen or sulfo; B is a general formula

Group or structural formula

Wherein R ₆ is hydrogen, chlorine, sulfo, carboxy, methyl, methoxy or ethoxy, X ₂ is lower alkoxy, unsubstituted or substituted phenoxy, or a general formula

R ₇ and R ₈ are each independently hydrogen or an unsubstituted or substituted lower alkyl, phenyl, naphthyl or benzyl group; A represents an unsubstituted or substituted phenylene or naphthylene group, Z represents a group of -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ Y, wherein Y can be removed by the action of an alkali Group. 18. The compound of claim 17, wherein R ₁ and R ₂ each independently represent hydrogen or methyl or ethyl, and A is unsubstituted or selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo or A process for preparing a monoazo compound of general formula (I ″), which represents phenylene substituted by two substituents, or naphthylene unsubstituted or substituted by one sulfo. The compound of claim 17, wherein Z is —SO ₂ CH═CH ₂ , —SO ₂ CH ₂ CH ₂ OSO ₃ H, —SO ₂ CH ₂ CH ₂ SSO ₃ H, —SO ₂ CH ₂ CH ₂ OPO ₃ H ₂ or -SO ₂ CH ₂ CH ₂ represents OCOH ₃ , X ₂ is a general formula

And a group of wherein R ₉ is hydrogen or methyl or ethyl. 18. The compound of claim 17 wherein B is

(Herein, the asterisk is the group

To a monoazo compound of formula (I ″).